Surface active agent and the process of treating fibrous materials therewith



Patented June 1, 1943 UNITED STATES PATENT OFFICE SURFACE ACTIVE AGENTAND THE PROCESS OF TREATING FIBROUS MATERIALS THEREWITH mu Robinette,Terre Haute, Ind., assignor to Commercial Solvents Corporation,'I'erreHaute,

' Ind., a corporation of Maryland No Drawing.

My invention relates to new and useful sur-' face active substances, andmore particularly 'it is concerned with a series of compounds, thegeneral type of which has never been, to my knowledge, recognized aspossessing wetting and penetrating properties,.as well as other surfaceactive characteristics. These compounds may be represented by thefollowing structural formula:

c c on, A

wherein R represents an alkyl group contain vng at least flve carbonatoms, and R is an alkyl group. I

Specific examples of the substituted 13-611- Application November 15,1941, Serial No. 419,318

7 cams. (01. 252-255) which is insoluble in water, is liberated. Instrongly alkaline solutions, on the other hand, ordinary soaps becomeinsoluble and are salted out of solution. In addition, in the presenceof solutions containing calcium or magnesium salts such as ordinary hardwater, the fatty acid present in the soap is precipitated as a calciumor magnesium soap, such soaps being insoluble sticky materials which,rather than having any detergent action, are regarded as undesirableimpurities in solutions employed in the textile and related industries.

In an effort to furnish materials to such ind'ustries free from theundesirable properties of ordinary soaps, there have beendeveloped asdetergent and wetting agents products obtained by the sulfonation ofcertain fatty acids ooixanes which belong to the class represented by.ction, such as the effect obtained by the presace of a surface activeagent at a water-oil nterface. For example, in the textile andeather-treating industries there are many sitcurring in 011s and fats.Such fatty acids are characterized by containing unsaturated linkagesand/or hydroxyl groups in the molecule.

On sulfonating such acids, products, are obtained which contain sulfuricacid ester groups in the molecule, and of course carboxylic acid groupsare attached to the terminal carbon atom. The products, however, ingeneral possess weaker wetting and detergent, properties than soaps.

lRtiOlilS where wetting or detergent action is lighly desirable. As aresult, many different gents have been proposed to reduce surface ensionand promote wetting. The materials reviously employed, however, althoughsatisfacary in some respects, have not met with unqualied success in allcases.

The ordinary soaps, although their surface ctive properties have longbeen recognized, are

eficient in many respects when employed in the eld of detergent andwetting agents. 'For exmple, although soaps act efficiently as deterentsin weakly alkaline solutions, they are of 0 value for this purpose inacid solutions, since nder such circumstances the free fatty acid,

Such products are also relatively unstable, and are capable of beingdecomposed by hydrolysis.

Other proposed wetting agents comprise the semiand completely-esterifiedproducts resulting from the esterification of a higher alcohol with anunsaturated pclybasic acid. After the unsaturated esterifled acid isproduced, it is converted into a, more soluble form, ordinarily bytreatment with sodium bisulfite to yield the corresponding sulfoderivative of the esterified polybasic acid. While such materials havemet with a considerable degree of success in various industries wherethe need for surface-active materials exists, they are not withoutdefects. 0bviouslv, surface-active agents of this type are not stable toalkali, and in some instances,

especially in the textile field, much difficulty has been experiencedwith the tendency of the textile-treating baths containing suchmaterials, to foam.

I have now discoveredthat the aminodioxanes included by the abovegeneric formula, when employed with a suitable solubilizingagent,.impart valuable surface-active properties to solutions thereof.Such wetting agents have been found to be particularly useful underconditions where previous wetting and penetrating agents. especially ofthe'type mentioned above, are of little or no value. For example, thewetting percent aqueous sulfonated parts of the aminodioxane.

i agents of the present invention are not decomposed either by hardwater, or solutions containing appreciable quantities of alkali. Thesenew wetting agents possess the further advantagein that aqueoussolutions thereof do not foam.

In general. the quantity of aminodioxanes that may be employed, will befound to vary with the type of wetting operation under consideration, aswell as with the material to be wetted. For the greater majority ofuses, however, I

power of the resulting solution was then measured at 30 C. by the methodof Draves and Clarkson, the following data being obtained:

have found that the aminodioxanes are most advantageously employed inamounts of from about .09 to 2.0 per cent by weight of the treatingbath. The quantity of solubilizing material to be utilized in preparingthe wetting agents of the present invention, will also be found todiffer, depending of course upon the type of solubilizing agent employedand the character oi the substance which is to be treated. Generally, Ihave found it suitable to employ the solubilizing agent in amountsvarying from approximately 10 to 35 per cent, based upon the weight ofthe aminodioxane used. As examples of suitable solubilizing materialswhich may be employed in preparing the wetting agents of the presentinvention, there may be mentioned sulfonated castor oil, sulfonatedpetroleum oils, sulionat'ed aliryl aromatic compounds, sulfated esters.sulfated ether alcohols, sulfonated alkyl diphenyls, and the like.

The wetting and penetrating powers of certain of, the wetting agentscovered by the present invention have been compared with some of thecommercially-available agents, the results of the tests performedappearing in the table below. The wetting properties of the variousagents tested were measured by the method of Draves and Clarkson (Am.Assoc. Textile Colorists and Chemists Year Book, vol. 17, pp. 216-222(1940)) which determines the sinking or wetting-out time required for afive-gram skein of unboiied two-ply yarn in varying concentrations ofaqueous solutions of wetting agents. These tests were performed at atemperature of approximate- Aminodioxanes of the type mentioned abovewere solubilized by blending 120 parts of 14.5 castor oil with 50 Thesinking times of aqueous solutions containing three grams per liter ofthe blend of certainof the aminodioxanes, are shown in the followingtable:

Grams per liter Instantaneous.

Example H 5 5-amino 5 ethylda-heptyl)-1,3-dioxane was found to have awetting time of 2,1 seconds in concentrations of 1.5 grams per liter at25 0..

according to the Braves test. The wetting time is instantaneous at aconcentration of 3 grams per liter in distilled water. In water of 18grains hardness, the solution exhibited a wetting time of 32 seconds ata concentration of 1.5 grams per liter, and 23, seconds at 3 gramsperliter. Triton W-30 alone possessed a wetting time of 8'? seconds at1.5 grams per liter, and 37 seconds at a concentration of 3 grams perliter.

Ewample H2 7 Grams per liter Wettlngout time 6 12 seconds. 5 15 seconds.2 SOscconds. 0' ..1 seconds.

Under similar conditions the wetting power of solutions containing onlySantomerse No. 1, in varyingconcentrations, were found to have thefollowing wetting-out activity when measured according to the method ofDraves and Clarlrson:

Wettingout time 6.2 seconds. 12.0 seconds.

Table I Wetting agent Wetting-out time5-amino-5-methyl-2-(3-hcptyl)-l,3-dioxane.. Skcin sinks instantly.G-aaIjiino'Ii-cthyI-Z-(l-cthyl-l-pentenyl)-1,3- 36 seconds. 60

oxane. 6-amino-6-cthyl-2-(3heptyl)-l,s4lioxane.... Skein sinksinstantly. ii-amino-5-ethyl-2-hendecyi-i,3-dioxane. 60 seconds.

acteristics of solutions containing commercially-available wettingagents.

\ Example I 34 seconds.

It will be apparent fromthe above data that that addition of5-amino-5-ethyl-2-(3-heptyl) 1,3-dioxane to a formula using SantomerseNo. 1

gives a much faster wetting time than aqueoussolutions containing onlySantomerse No. 1. For example. 6 grams per liter of the wetting agentcontaining both 5-amino-5-ethyl-2-(3-heptyl)- 1,3-dioxane andSaritomerse No. 1 is equivalent to .84 gram per liter of SantomerseNo. 1. The

former wetting agent, in concentrations of 6 grams per liter, gives a.solution possessing a wettingtime of 12 seconds, whereas a solutioncontaining. gram per liter oi Santomerse No. 1

possesses a wetting time which is appreciably excess of 34 seconds.

The aminodioxanes of the present invention may be prepared in accordancewith any ofsev- Over Bminutes.

eral suitable procedures. I prefer, however, to produce such materialsby means-of the process described in U. S. Patent No. 2,247,256 grantedJune 24, 19.41, to Murray Senkus. According to this procedure, thecorresponding nitrodioxane is subjected to high-pressure hydrogenationin the presence of a nickel catalyst and a suitable solvent, such asmethanol, at a temperature in the neighborhood of 25-30 C. Thestartingmaterials in this process are conveniently prepared bycondensing a suitable poly-hydroxy nitro compound with an aliphaticaldehyde, such as hexanal, heptanal, heptaldehyde, 2-ethyl-hexanal,dodecanai, and the like. This condensation reaction is carried out byheating the polyhydroxy nitro compound in the presence of the desiredaldehyde and a small quantity of an acid catalyst, and if desired, inthe presence of an organic liquid, such as benzene or toluene, which iscapable of removing the water produced during the reaction in the formof a constant boiling mixture.

In regard to the siiigle compounds covered by certain of the appendedclaims, these products,

. i. e., -amino-5-methy1-2-( -heptyl) -1,3-dioxane and5-amino-5-ethyl-2- (3-hepty1) -1,3 -dioxane, may be prepared by firstsynthesizing the corresponding nitrodioxane, which in the case of theformer compound involves the condensation of 1 mole of2-methyl-2-nitro-1,3-propanediol with 1 mole of 2-ethylhexanal, whilethe latter amino dioxane requires the condensation of 1 mole of2-ethy1-2-nitro-1,3-propanediol with 1 mole of 2-ethyl-hexanal. Bothcondensation reactions require the presence of a small quantity of amineral acid, such as sulfuric acid to serve as a catalyst. Therespective nitro dioxanes, prepared in this manner, are then dissolvedin a suitable solvent such as methanol and subjected to the action ofhydrogen at a temperature of 25-30 0., and at a pressure of 2000 poundsper square inch in the presence of Raney nickel, to produce thecorresponding amino dioxan'e.

It is understood that applicant does not claim the amino dioxanes per sedescribed and referred to herein but instead claims merely the new andnovel use of said compounds which is disclosed herein.

Wetting agents of the type contemplated by the present invention areespecially suited for use in the preparation of printing pastes andsizing mixtures. They may also be used as penetrants in fiax-rettingbaths. These products serve as useful wetting, cleansing, andpenetrating agents in bleaching liquors, such as those used in kierboiling of cotton goods, and may be added to the lye liquors used formercerizing cotton goods. They can also be used to assist in twistsetting of yarn and in processes of stripping colors. Such compoundsalso find use as assistants in processes of stripping dyes from dyedtextile material.

A second class of uses of these new surfaceactive agentsconstitutestheir use as assistants in the application of dyestuffs. Theymay be employed as dye-leveling agents due to their wetting andpenetrating powers in neutral or alkaline dyeing baths, and are capableof facilitating dyeing with developed dyes, the dyeing of acetate fiberswith insoluble dyes, the dyeing of animal fibers with vat dyes, thedyeing of various synthetic fibers, and the dyeing of leather.

It will readily be seen from the foregoing description that by'means ofthe present invention, a large group of new surface-active substanceshas been made available, and that such agents are adapted for use innumerous industrial processes which require surface-active materials. Itwill also be apparent to those skilled in the art that many widelydifferent embodiments of the present invention exist, and that suchembodiments may be utilized without departing from the scope of saidinvention. v

My invention now having been described, what I claim is:

1. A bath for the wet treatment of organic fibrous materials to changethe surface active properties thereof, comprising an added solubilizingcompound of the sulfur-containing type and an aminodioxane having theformula:

in which R represents an alkyl group containing at least 5 carbon atoms,and R is an alkyl group.

3. An aqueous bath for the wet treatment of organic fibrous materialstochange the surface active properties thereof, comprising an added'solubilizing compound of the sulfur-containing type and from about 0.09to 2 per cent by weight of the bath of an aminodioxane having theformula:

wherein R represents an alkyl group containing at least 5 carbon atoms,and R. is an allq'l group.

4. An aqueous bath for the wet treatment of organic. fibrous materialsto change the surface active properties thereof, comprising an addedsolubilizing compound of the sulfur-containing type and5-amino-5-ethyl-2-(3-heptyl);1,3-dioxane.

. 5. In the process for the wet treatment of organic fibrousmaterialsrin an aqueous bath to improve the surface active propertiesthereof, the improvement which comprises incorporating in the bath in anamountto change its surface active properties a composition consistingof an wherein R represents an alkyi group having at least 5 carbonatoms, and R is an alkyl group.

6. In the process for the wet treatment of organic fibrous materials inan aqueous bath to improve the surface active properties thereof, the 15improvement which comprises incorporating in the bath in on amount toohmic its surisce sctive properties e composition consisting of an addedsoiubiiisinz scent of the miiur-ccntsinins type and fismino-i-ethyi-z-(ii-heptyi)-i.3-diossne.

7. In the process for the wet treatment 0! organic nbrous materials inan aqueous both to improve the surisce active properties thereof, theimprovement which comprises incorporating in the bath in an' amount tochange its surisce active properties a composition consisting of anadded soiubiiizin: scent oi the sulfur-conteininz type and5-amino-5-methyl-2-(3-heptyi) -1,3-dioxsne.

HILLARY ROBINE'II'E.

